اصلاح شیمیایی لیگنین: گامی به سمت سنتز پلی‌ال

نوع مقاله: تالیفی

نویسندگان

1 دانشجوی کارشناسی ارشد/ دانشگاه تربیت مدرس

2 عضو هیات علمی/ دانشگاه تربیت مدرس

چکیده

در چند دهه گذشته، مقالات زیادی در ارتباط با توسعه لیگنین منتشر شده که بیشتر در باره اصلاح شیمیایی لیگنین بوده است. استفاده از لیگنین به‌طور مستقیم، اغلب به سنتز و تولید مواد کم ارزش منجر می‌شود. از این رو، اصلاح شیمیایی لیگنین، نه‌تنها موجب افزایش واکنش‌پذیری آن ‌شده، بلکه موجب پخش بهتر آن در مواد پلیمری می‌شود. ساختار شیمیایی لیگنین شامل واحدهای فنیل پروپان است که از سه ترکیب پیش‌ساز آروماتیکی و الکلی پاراکوماریل الکل، کانیفریل الکل و سیناپیل الکل ناشی می‌شود. لیگنین با دو روش استفاده می‌شود. در روش اول، لیگنین بدون اصلاح شیمیایی برای بهبود خواص مد نظر به ماتریس پلیمری افزوده می‌شود. اما در روش دوم، با اصلاح شیمیایی لیگنین و
آماده‌سازی آن برای سنتز طیف گسترده‌ای از مواد پلیمری استفاده می‌شود. اصلاح شیمیایی لیگنین بارها برای اهداف مختلف مطالعه شده است. اصلاح لیگنین از راه واکنش با فرمالدهید، اپی‌کلروهیدرین، فنول، پروپیلن اکسید، پروپیلن کربنات، پلی‌اتیلن گلیکول و سنتز کوپلیمرهای بر پایه لیگنین از جمله واکنش‌هایی هستند که بحث و بررسی شده‌اند. با این حال، این مقاله به بحث در باره اصلاح شیمیایی لیگنین و استفاده از آن به‌عنوان منبع مونومر در فرایند پلیمرشدن، محدود شده است.

کلیدواژه‌ها

موضوعات


عنوان مقاله [English]

Chemical Modification of Lignin: A Step Toward Synthesis of Polyol

نویسنده [English]

  • Mahdi Abdollahi 2
چکیده [English]

In the recent decades, many articles have been published on the development of lignin and mostly related to the chemical modification of lignin.The direct use of lignin often leads to the synthesis and production of low-value added materials. Hence, chemical modification of lignin not only increases its activity in the reactions but also represents a fine dispersion in the polymer materials. Chemical structure of lignin contains phenyl propane units, originating from three aromatic alcohol precursors of p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. The main uses of lignin can be classified into two different methods. In the first method, without chemical modification, lignin is directly incorporated into a polymer matrix to give new or improved properties. In the second method, a large range of polymer materials is synthesized via chemical modification of the lignin. Chemical modification of the lignin has been studied frequently for various purposes. Lignin modification through reaction with formaldehyde, epichlorohydrin, phenol, propylene oxide, propylene carbonate, polyethylene glycol and synthesis of lignin-based copolymers are among reactions studied in the literature. However, this article has been restricted to the discussion on chemical modification of lignin and its use as a source of monomer in the polymerization process.

کلیدواژه‌ها [English]

  • lignin
  • chemical modification
  • polyol
  • condensation polymerization
  • polyurethane
1.Yang L., Wang X., Cui Y., and Tian Y., Modification of RenewableResources Lignin by Three Chemical Methods and Its Applications to Polyurethane Foams, Polym. Adv. Technol., 25, 1089-1098, 2014.
2.Liu J., Liu H., Deng L., Liao B., and Guo Q., Improving Aging Resistance and Mechanical Properties of Waterborne PolyurethanesModified by Lignin Amines, Chem. Rev., 130, 1736-1742, 2013.
3.Sewalt V., Glasser W., and Beauchemin K., Lignin Impact on Fiber Degradation.3. Reversal of Inhibition of Enzymatic Hydrolysis by Chemical Modification of Lignin and by Additives,J. Agric. Food. Chem., 45, 1823-1828, 1997.
4.Marton J., Lignin Structure and Reactions, Adv. Chem., 59, 263-267, 1966.
5.Phillips M., The Chemistry of Lignin, Chem. Rev., 14, 103-170, 1934.
6.Benedikt R. and Bamberger M., Über Eine Quantitative ReactionDeslignins, Monatsh. Chem., 11, 260-267, 1890.
7.Adler E., Lignin Chemistry-Past, Present and Future, Wood. Sci. Technol., 11, 169-218, 1977.
8.Freudenberg K., Biosynthesis and Constitution of Lignin, Nature,183, 1152-1155, 1959.
9.Chakar F. and Ragauskas A., Review of Current and Future Softwood Kraft Lignin Process Chemistry, Ind. Crops. Prod., 20, 131-141, 2004.
10.Freudenberg K., Lignin: Its Constitution and Formation From p-Hydroxycinnamyl Alcohols, Science, 48, 595-600, 1965.
11.Laurichesse S. and Avérous L., Chemical Modification of Lignins: Towards Biobased Polymers, Prog. Polym. Sci., 39, 1266-1290, 2014.
12.Hatakeyama H., Nakano J., and Hatano A., Variation of InfraredSpectra with Temperature for Lignin and Lignin Model Compounds, Tappi Technol. Ass. Pulp Pap. Indus., 52, 1724-1728, 1969.
13.Nassar M. and MacKay G., Mechanism of Thermal Decompositionof Lignin, Wood Fiber Sci., 16, 441-453, 1984.
14.Malutan T. and Nicu R., Contribution to The Study of HydroxymetylationReaction of Alkali Lignin, Macromolecules, 3, 13-20, 2008.
15.Cetin N. and Ozmen N., Studies on Lignin-Based Adhesives for Particleboard Panels, Turk. J. Agric., 27, 183-189, 2003.
16.Malutan T. and Nicu R., Lignin Modification by Epoxidation, Bioresources, 3, 1371-1376, 2008.
17.Hu L., Pan H., and Zhou Y., Methods to Improve Lignin’s Reactivityas Aphenol Substitute and as Replacement for Other Phenolic Compounds: A Brief Review, Bioresources, 6, 3515-3525, 2011.
18.Cateto C.A., Barriero M.F., Rodrigues A.E., and Belgacem M.N., Optimization Study of Lignin Oxypropylation In View of the Preparation of Polyurethane Rigid Foams, Ind. Eng. Chem., 48, 2583-2589, 2009.
19.Arshanitsa A., Paberza A., Vevere L., and Cabulis U., Two Approachesfor Introduction of Wheat Straw Lignin into Rigid Polyurethane Foams, AIP Conference Proceedings, 1593, 388-391, 2014.
20.Kühnel I., Podschun J., Saake B., and Lehnen R, Synthesis of Lignin Polyols via Oxyalkylation with Propylene arbonate, Holzforschung, 69, 531–538, 2015.
21.Yanming H., Tefu Q., and Fuxiang C., Preparation and Propertiesof Polyurethane Heat Insulating Building Materials Based on Lignin, Appl. Mech.Mater., 193, 505-508, 2012.
22.Pouteau C., Baumberger S., Cathala B., and Dole P., Lignin-Polymer Blends: Evaluation of Compatibility by Image Analysis,Comptes. Rendus. Biol., 327, 935–943, 2004.
23.Chen S., Liu M., Jin S., and Chen Y., Synthesis and Swelling Properties of pH-sensitive Hydrogels Based on Chitosan and Poly(methacrylic acid) Semi-interpenetrating Polymer Network,J. Appl. Polym. Sci., 98, 1720–1726, 2005.
24.Teramoto Y., Lee S., and Endo T., Molecular Composite of Lignin: Miscibility and Complex Formation of Organosolv Lignin and Its Acetates with Synthetic Polymers Containing Vinyl Pyrrolidone and/or Vinyl Acetate Units, J. Appl. Polym. Sci., 125, 2063–2070, 2012.
25.Yue X., Chen F., Zhou X., and He G., Preparation and Characterizationof Poly(vinyl chloride) Polyblends with FractionatedLignin, Int. J. Polym. Mater., 61, 214–228, 2012.
26.Duval A. and Lawoko M., A Review on Lignin-Based Polymeric,Micro- and Nano-structured Materials, React. Funct. Polym., 85, 78–96, 2014.
27.Kubo S. and Kadla J., The Formation of Strong Intermolecular Interactions In Immiscible Blends of Poly(vinyl alcohol) (PVA) and Lignin, Biomacromolecules, 4, 561–567, 2003.

28.Meister J., Lathia A., and Chang F., Solvent Effects, Species and Extraction Method Effects, and Coinitiator Effects in the Grafting of Lignin, J. Polym. Sci., Polym. Chem., 29, 1465-1473, 1991
29.Jia Z., Lu C., Zhou P., and Wang L., Preparation and Characterizationof High Boiling Solvent Lignin-Based Polyurethane Film With Lignin as the Only Hydroxyl Group Provider, RSC. Adv., 5, 53949-53955, 2015.
30.Saito T., Perkins J.H., Jackson D.C., Trammel N.E., Hunt M.A., and Naskar A.K., Development of Lignin-Based PolyurethaneThermoplastics, RSC. Adv., 3, 21832-21840, 2013.